This invention relates to a process for forming clay catalysts that can be used in a catalyst system for the polymerization of xcex1-olefins. In one aspect, the present invention relates to novel polymerization catalysts. In another aspect, the present invention relates to a process for polymerizing xcex1-olefins. In yet another aspect, this invention relates to novel polymers of xcex1-olefins.
The preparation of pillared interlayer clay compositions by reacting a smectite-type clay with an aqueous solution of suitable polymeric cationic hydroxy metal complexes of metals, such as aluminum, titanium, zirconium and chromium is known, as illustrated in U.S. Pat. Nos. 4,665,045, 4,742,033, herein incorporated by reference. Further, U.S. Pat. No. 4,665,045, Pinnavaia et al. discloses that such pillared interlayed clay compositions that are prepared with chromium can be used in olefin polymerization.
However, there is an ever present need to develop pillared interlayered clays with new processes that result in different catalysts. Equally important is the need to develop a process to produce efficient clay catalysts on a commercial scale. Further, a better understanding of the considerable diversity within this group of clays is needed such that the type of polymers produced can be explored for special or unique properties.
It is therefore an object of this invention to provide a novel method for preparing catalyst compositions.
It is another object of this invention to provide a novel catalyst composition well-adapted for the polymerization of xcex1-olefins.
It is still a further object of this invention to provide an improved process for the polymerization of xcex1-olefins.
These and other objects of the present invention will become apparent from the disclosure and claims herein provided.
In accordance with the present invention, there is provided a novel method for preparing a new catalyst composition efficient for use in the polymerization of xcex1-olefins by preparing a pillared phyllosilicate clay comprising the following steps of:
(a) preparing a hydrolyzed first solution by dissolving a chromium salt and a base in water, heating said first solution to a temperature in the range of about 20xc2x0 C. to about 100xc2x0 C. while stirring continuously until the solution reaches a pH in the range of about 1.5 to about 2.5 and thereby producing a master batch;
(b) diluting said master batch with water to produce a diluted second solution and heating said diluted second solution to produce a heated second solution;
(c) adding a solid phyllosilicate lay selected from the group consisting of dioctahedral and trioctahedral smectites to said heated second solution, and continuing heating;
(d) recovering said pillared phylloilicate clay; and
(e) drying said pillared phyllosilicate clay to form a first product.
In a further embodiment there is provided the activation of said clay comprising the following steps of:
(a) heating said first product at a temperature in the range of about 150xc2x0 C. to about 500xc2x0 C. and for a time period in the range of about 30 minutes to about 10 hours in an inert atmosphere;
(b) thereafter heating said first product at a temperature in the range of about 500xc2x0 C. to about 900xc2x0 C. and for a time period in the range of about 1 hour to about 50 hours in an oxidizing atmosphere and recovering said catalyst composition.
In further accordance with the present invention, there is provided an improved method for the polymerization of xcex1-olefins which results in novel polymer compositions and which comprises: contacting at least one mono-1-olefin having 2 to 8 carbon atoms per molecule with said catalyst; optionally copolymerizing with a conomomer having from about 3 to about 8 carbon atoms per molecule; and optionally combining said catalyst with an organo-metal cocatalyst.
General Preparation of Chromium-Pillared Clays
The clays employed in the present invention are the dioctahedral and trioctahedral smectites which have a platelet morphology containing extended sheets of silica tetrahedra and alumina octahedra (smectites) or sheets of silica tetrahedra and magnesia octahedra joined together. The natural abundance and commercial availability of clays make them an inexpensive alternative to more costly synthetic silicas presently used for olefin polymerization.
The method employed consists of considerable modifications to the process disclosed in Pinnavaia et al of U.S. Pat. No. 4,665,045. One differentiating factor is that Pinnavaia is limited to xe2x80x9c. . . an aqueous slurry of a layer lattice clay.xe2x80x9d The present invention provides a novel process for preparing a pillared phyllosilicate clay; the first step of which is preparing a hydrolyzed first solution by dissolving a chromium salt and a base in water, heating said first solution to a temperature in the range of about 20xc2x0 C. to about 100xc2x0 C. while stirring continuously until the solution reaches a pH in the range of about 1.5 to about 2.5 and thereby producing a master batch. The heating accomplishes in a reasonable time the hydrolytic polymerization of chromium while the pH indicates when to stop heating so as to optimize the concentration of the highly polyhydroxy chromium oligomers. Using the pH of said first solution to determine when heating Is sufficient is a novel method of accomplishing what is referred to in prior patents as xe2x80x9cagingxe2x80x9d. Preferably, the heating is conducted at a temperature of about 90xc2x0 C. while stirring continues until said first solution reaches a pH of about 2.3.
Said base is selected from the group consisting of sodium carbonate, ammonium carbonate, sodium hydroxide and ammonium hydroxide with preference given to sodium carbonate. Said salt is selected from the group consisting of chromium nitrate and chromium acetate with preference given to chromium nitrate.
The second step is diluting said master batch with water to produce a diluted second solution and heating said diluted second solution to produce a heated second solution. It was discovered that achieving a diluted said master batch facilitates the goal of producing said pillared phyllosilicate clay on a commercial scale.
Pinnavaia discloses the preparation of a clay slurry to be contacted with a chromium solution. In accordance with the present invention, said master batch containing chromium in solution is diluted and dry (i.e. powdered or free flowing) clay is added. When said pillared phyllosilicate clay is prepared on a commercial scale the liquid volume required to slurry such quantities is too great to be viable. It is unexpected that by diluting said master batch in lieu of slurrying said clay, the liquid volume required is reduced to less than one-fourth of that otherwise required.
The dilution step also provides a means whereby the chromium content of the final catalyst can be controlled. When known methods of preparing pillared phyllosilicate clays are used, the final clay product is high in chromium content; and when this product is utilized as a polymerization catalyst, an unacceptably high amount of Cr(VI) is present. Possible health hazards associated with Cr(VI) are diminished when the initial chromium content is controlled via the method of the present invention.
Said dilution is carried out such that said first solution is diluted to the ratio of about 0.5 ml H2O to about 10 ml H2O to about 1 ml master batch, with a preferred amount of H2O being 4 mls H2O to about 1 ml master batch. Said said second solution is heated to a temperature in the range of about 20xc2x0 C. to about 100xc2x0 C. with a preferred heating at about 90xc2x0 C.
The third step comprises adding a solid clay selected from the group consisting of dioctahedral and trioctahedral smectites to said heated second solution. The clay is added in solid form for the reasons set out supra. The liquid volume of said second solution is in the range of about 1 ml to about 50 mls per gram of clay and contains an amount of chromium in the range of about 0.001 grams to about 0.01 grams per ml of said second solution, with a preferred volume of said second solution being about 5 mls per gram of clay and containing about 0.002 grams of chromium per ml of said second solution.
The novel pillared clay may be recovered by conventional methods well known to those skilled in the art. However, it is preferred that said pillared phyllosilicate clay be washed and centrifuged with an initial series of washes being conducted with H2O and a secondary series of washes being conducted with an alcohol for the purpose of removing unbound H2O before the final drying step and thereby minimizing the collapse of the clay pore structure due to the surface tension of the H2O during the drying process. This produces a first product which is thereafter dried using any method known to those of skill in the art such as oven or vacuum, or freeze drying. Other methods to remove water include but are not limited to azeotrope drying or spray drying.
The dried chromium pillared clays can be activated to achieve a catalyst system by performing the following steps which comprise:
(a) heating said first product at a temperature in the range of about 150xc2x0 C. to about 500xc2x0 C. and for a time period in the range of about 30 minutes to about 10 hours in an inert atmosphere, with a preferred temperature of about 500xc2x0 C. for a time period of about 1 hour;
(b) thereafter heating said first product at a temperature in the range of about 500xc2x0 C. to about 900xc2x0 C. and for a time period in the range of about 1 hour to about 50 hours in an oxidizing atmosphere and recovering a second product, with a preferred temperature of about 650xc2x0 C. for a time period of about 3 hours.
Optionally, the activation may further comprise cooling said second product to a temperature in the range of about 300xc2x0 C. to about 500xc2x0 C. and for a time period in the range of about 1 minute to about 5 hours in a reducing atmosphere, with a preferred temperature of 350xc2x0 C. for a time period of about 30 minutes. The optional heating accomplishes a more productive olefin polymerization catalyst than that which can be made via one-step continuous heating.
The polymerization process of the present invention requires that at least one mono-1-olefin having 2 to 8 carbon atoms per molecule be contacted with said novel catalyst system. The olefin is selected from the group consisting of ethylene, propylene, 1-pentene, 1-hexene, and 1-octene. Preferably said olefin is predominantly ethylene.
A comonomer may be copolymerized with ethylene to form an ethylene copolymer. Said comonomer can be selected from the group consisting of propylene, 1-butene, 1-pentene, 1-hexene, and 1-octene. Preferred copolymers are those of ethylene and 0.4 to 1 weight percent of a comonomer selected from C4 to C12 mono-1-olefins, most preferably hexene.
Additionally, said novel catalyst system may be combined with an organo-metal cocatalyst selected from the group consisting of: triethylaluminum, triethylboron, and diethylsilane. Preferred cocatalyst is triethylaluminum.